Dynamical Line-Shifts in High-Field Electron Spin Resonance: Applications to Polymer Physics

High-field high-frequency Electron Paramagnetic Resonance spectroscopy (HP-EPR) is a powerful tool to investigate, with ultra-high angular resolution, the rotational dynamics of complex systems like polymers, viscous fluids and glasses. Usually, information is drawn by detailed numerical analysis of the overall lineshape. Here, we present a simplified analytical model of the line shifts due to the rotational dynamics of the paramagnetic centre. The model captures the basic features of the reorientation process (time scale and size of the angular jump). It is compared with experimental results concerning the reorientation of a paramagnetic guest molecule dissolved in polystyrene. We find that, if the rotational model to describe the reorientation of the radical is consistent, the best-fit parameters yield equally acceptable best-fits of the overall spectrum by numerical simulations and dynamical line shifts by independent analytic expressions.